The concerted PT picture is updated via considering both exact exchange
and van der Waals interactions in AIMD simulations. [1]}.
By utilizing the hybrid functional PBE0 [2]} with
the self-consistent Tkatchenko-Scheffler (TS) functional in AIMD simulations, [3]}, [4]}
the so-called PBE0-TS exchange-correlation functional mitigates the spurious self-interaction and includes both intermediate- and long-range van der Waals interactions. This leads to a better description of the H-bond network of liquid water,
where structural and dynamic properties of \(\rm OH^{-}\) (aq) and \(\rm H_{3}O^{+}\) (aq) are
substantially improved towards the experimental data.
For example, while previous AIMD simulations utilizing GGA functionals
suggested that the hydroxide has a planar solvation structure, [5]}, [6]}
the PBE0-TS predicted a pot-like solvation structure of hydroxide that agrees with the
picture from neutron scattering data. [7]}, [1]}
In addition, unlike BLYP, the PBE0-TS functional largely stabilized the 4-fold solvation structure of \(\rm OH^{-}\) (aq),
which inhibits the concerted PT behaviors of hydroxide.
Instead, the solvated hydroxide ion described by PBE0-TS exhibits a stepwise motion.
Meanwhile, \(\rm H_{3}O^{+}\) (aq) still preserves
the concerted PT behavior within the description of PBE0-TS. Consequently, PBE0-TS predicts
a slower diffusivity of hydroxide than hydronium, [1]} which agrees well with the experiments. [10]}, [11]}, [12]}
